WO1995031514A1 - Colle hydrophile autocollante composite et son procede de preparation - Google Patents

Colle hydrophile autocollante composite et son procede de preparation Download PDF

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Publication number
WO1995031514A1
WO1995031514A1 PCT/CZ1995/000007 CZ9500007W WO9531514A1 WO 1995031514 A1 WO1995031514 A1 WO 1995031514A1 CZ 9500007 W CZ9500007 W CZ 9500007W WO 9531514 A1 WO9531514 A1 WO 9531514A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
polymer
polar
atmospheric pressure
temperatures higher
Prior art date
Application number
PCT/CZ1995/000007
Other languages
English (en)
Inventor
Jir^¿í S^¿ULC
Zuzana KRC^¿OVÁ
Original Assignee
Sulc Jiri
Krcova Zuzana
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sulc Jiri, Krcova Zuzana filed Critical Sulc Jiri
Priority to SK1276-2000A priority Critical patent/SK281917B6/sk
Priority to DE69503898T priority patent/DE69503898T2/de
Priority to EP95917255A priority patent/EP0759054B1/fr
Priority to US08/732,477 priority patent/US5807917A/en
Priority to SK1431-96A priority patent/SK281916B6/sk
Priority to JP7529273A priority patent/JPH10500158A/ja
Publication of WO1995031514A1 publication Critical patent/WO1995031514A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/07—Microporous membranes

Definitions

  • the invention relates to a composite pressure sensitive adhesive particularly suitable for temporary glueing medical and cosmetic means to the body surface from which it can be easily removed by liquid water or by innocuous diluted aqueous solutions.
  • non-tacky hydrogel covers of burnt or wounded skin consisting of a gelled mixture of water-insolu ⁇ ble, water swellable polymers such as poly(2-hydroxyethyl methacrylate) , which can be either covalently crosslinked (three-dimensional) or solvent soluble noncrossiinked, with polar high boiling solvent such polyethylene glycol, preferably mixed with water either by sprinkling the liquid component onto skin and then powdering it with the ground dried polymer, or by mixing the two components just before the spreading.
  • the mixture sets af-ter a short spell up to about 50 minutes, forming a non-tacky layer which can be peeled off as such or after further wetting.
  • all components are water - soluble and the mixture has to be heated in the presence of water to at least 95°C to form a melt capable to get gelled only upon cooling.
  • the preparation requi ⁇ res a temperature-controlled stirrable reactor and temperatures up to 130°C. No crosslinked or insoluble polymer is added. The mixture is set by cooling, not by heating.
  • the object of the present invention is a composite pressure sensitive hydrophilic adhesive. permeable for water vapor and losing its adhesivness in cont ⁇ t with liquid water, particularly suitable for temporary glueing medical means to the body surface, consisting of the gelled mixture of a (a) a water swellable, water insoluble polymer, soluble in polar water-miscible solvents, boiling at atmospheric pressure at temperatures higher than 100°C as well as in their mixtures with minor amounts of water, a (b) hydrophilic water swellable polymer, insoluble in water as well as in polar water-miscible solvents boiling at atmospheric pressure at temperatures higher than 100°C and a (c) a polar water-miscible inocuous solvent, boiling at atmospheric pressure at temperatures higher than 100°C, if desired mixed with a minor amount of water.
  • Another object of the invention is a composite pressure sensitive hydrophilic adhesive, permeable for water vapor, and losing its adhesivness in contact with liquid water, particu- larly suitable for temporary glueing medical means to the body surface, wherein the separate polymers (a) and (b) are replaced by a non-crosslinked copolymer of hydrophilic and hydrophobic monomers, only partially soluble in the component (c) but swellable therein.
  • the invention furthermore comprises a method of preparing the composite pressure sensitive hydrophilic adhesive according to the invention consisting in the short-time intensive stirring of the dry pulverized polymers (a) being- the water swellable, water insoluble polymer, soluble in polar water- miscible solvents boiling at atmospheric pressure at temperatu ⁇ res higher than 100°C as well as in their mixtures with minor amounts of water and (b) being the hydrophilic water swellable polymer, insoluble in water as well as in polar water-miscible solvents boiling at atmospheric pressure at temperatures higher than 100°C, in the solvent (c) being a polar water-miscible innocuous solvent boiling at atmospheric pressure at temperatu ⁇ res higher than 100°C, if desired mixed with a minor amount of water, spreading the paste thus obtained on a pad, and setting it to a gelled layer.
  • the dry pulverized polymers (a) being- the water swellable, water insoluble polymer, soluble in polar water- mis
  • the stirring of the components according to the method of the invention is carried out preferable at a temperature not exceeding 15°C and the setting of the stirred mixture is carried out at temperatures in the range of from about 15° to 100°C.
  • the inventive composite pressure sensitive hydrophilic adhesive can according to the invention be used in such a way that the mixing of components is with advantage carried out at temperatures not exceeding 15°C and the thus recieved mass is afterwards spread to the surface of the medical means to be glued to the body surface, and subseqently the spread layer is left to set at temperatures in the range of from 15°C to about 100°C either by prolonged storage at room temperature or by heating.
  • medical means comprises devices and means utilizable externaly in medicine, e.g. pouches with drug for transdermal application, contact with various medical measuring apparatures, special dressing, stopper-like means for restrai ⁇ ning urinary incontinence device etc.
  • polymer includes both homo- and copoly- itiers with purely carbonaceous or hetero-atoms containing main chain.
  • Most common examples of water-miscible, polar high-boiling innocuos liquids are glycerol and its partial esters such as glycerol mono- and diacetate, alkylene glycols such as ethylene and propylene glycols, dimethylsulfoxide.
  • the solubility of the polymers (a) in polar, water-misci- ble solvents is caused by the presence of hydrophilic side substituents or also of oxygen atoms in the main chain.
  • the insolubility of the polymers (b) is due usually to covalent crosslinking, in some cases also to the presence of hydrophobic comonomer units, although covalently crosslinked polymers such as poly(2-hydroxyethyl methacrylate) crosslinked by a small amount (up to about 2%) of ethyleneglycol dimethacrylate, or metha ⁇ rylamide copolymerized with a similary amount of ethyle- ne-bis-methacrylamide are prefered.
  • water swellable polymers (b) insoluble in water as well as in polar water miscible, high boiling solvents defined sub (c) and in their mixtures with water e. g. following ones can be used.
  • Copolymers of minor amount of hydrophobic monomers such as methylmethacrylate, butylacrylate and methacrylate, or vinylacetate, with a major amount of essentially nonionizable hydrophilic monomers, the hydrophility of which is caused by the content of free hydroxylic or other non-substituted or mono- or disubstituted amide groups, lactone, lactame, pyrroli- done etc. , provided of course that such copolymers are innocu- os.
  • the copolymer of this kind, belonging to the sort defined sub (b) can contain a small amount of units ionizable in water such as those acrylic, methacrylic or vinyl sulfonic acid in form of their sodium salts.
  • the adhesives of the invention can be prepared by grinding from about 0,2 parts to about 75 parts of dry polymer (a), a water swellable, water insoluble polymer, soluble in polar water-miscible solvents, boiling at atmospheric pressure at temperatures higher than 100°C as well as in their mixtures with minor amounts of water, with from about 2 to about 75 parts of dry polymer (b) , a hydrophilic water swellable polymer, insoluble in water as well as in polar water-miscible solvents boiling at atmospheric pressure at temperatures higher than 100°C to a fine powder which is rapidly stirred into from about 15 parts to about 90 parts of liquid (c), a polar water- miscible innocuous solvent, boiling at atmospheric pressure at temperatures higher than 100°C, if desired mixed with a minor amount of water, which has been preferably cooled under +5°C.
  • the intensive stirring lasts but several minutes and the mash thus obtained is spread onto a pad or a release sheet or foil such as siliconized or parafinized paper or Mylar foil. Thanks to the content of the insoluble, but swellable polymer (b) the not yet gelled mixture displays no tendency to cool flow and forms easily a uniform layer which is then set either by prolonged storage at room temperature or, better, by heating up to about 100°C. The gelled layer does not flow even at increa- sed temperatures.
  • the mixture of non-crosslinked and crosslinked polymers can be prepared either separately in two different batches, or also in one batch by first carrying out linear (or branched) polymerization and, prior to its end when the batch still contains the monomer and initiator and is still easily stirra- ble, by adding a suitable soluble cros ⁇ linking agent.
  • the ratio of the components (a) and (b) is chosen so as to obtain the required tackiness and elongation of the set or gelled adhesive. Said properties can be influenced in a known way by the ratio of high and low molecular weight of the poly ⁇ mer.
  • poly(2-hydroxyethyl methacrylate) poly(2-hydroxyethyl methacrylate)
  • the main advantage of the present adhesive lies in the absence of plastic cool flow due to the content of the polymer (b) , a hydrophilic water swellable polymer, insoluble in water as well as in polar water-miscible solvents boiling at at ⁇ mospheric pressure at temperatures higher than 100°C, particu ⁇ larly when the same is partly or sparingly crosslinked and/or but partially swellable in the component (c) a polar water- miscible innocuous solvent, boiling at atmospheric pressure at temperatures higher than 100°C, if desired mixed with a minor amount of water as well as in water.
  • the present adhesive is easily permeable for water vapors so that the skin does not sweat below it, provided that the medical means glued by it is also water vapor permeable.
  • the adhesive of the invention has good affinity to hydrophilic surfaces, e.g. to medical means to be adhered to the skin made from hydrophilic materials such as hydrophilic polyurethanes, to many metals, china etc. Adhesion to the otherwise hydrophobic polymers such as porous (micro- or macroporous) polyolefines can be achieved by chemical sulfona- tion or oxidation by means of silent discharge and neutraliza ⁇ tion.
  • Other examples of materials compatible with the present adhesive are various hydrogels and their composites such as polysiloxane/polyHEMA and others.
  • Dry powdered mixture of 22 g ethoxyethyl methacrylate polymer with 5g poly(2-hydroxyethyl methacrylate) crosslinked with 0.8g ethyleneglycol dimethacrylate is stirred at 15°C intensively for two minutes in 31 g of polypropyleneglycol (PPG 400)
  • PPG 400 polypropyleneglycol
  • the thin paste thus obtained is spread onto a foil of porous hydro ⁇ philic polyurethane and heated 30 minutes to 80°C.
  • the layer has high adhesivity to the skin and the whole can be easily removed by rinsing with water.
  • Example 4 30 g of the dry powdered copolymer of methyl methacrylate, hydroxyethyl methacrylate and methacrylic acid, ratio of the units 20:19:1, with an average molecular weight about 2xl0 5 , are stirred intensively for 3 minutes into 45 g of a mixture of polyethylene glycol PEG 400 with propylene glycol in a ratio of 80:20.
  • the paste is spread in an about 1 mm thick layer onto a foil of hydrophilic polyurethane and left 4 hours at room temperature.
  • the adhesive layer loses it ⁇ adhesiveness if brought in contact with a surplus of water.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Medicinal Preparation (AREA)

Abstract

Colle hydrophile autocollante composite. Cette colle est perméable à la vapeur d'eau et perd de son pouvoir adhésif au contact de l'eau liquide. En outre, elle est utilisable notamment dans le but de fixer provisoirement à la peau un dispositif à usage médical. Ladite colle comporte un mélange gélifié (a) d'un polymère non hydrosoluble gonflant au contact de l'eau et étant soluble dans les solvants polaires miscibles à l'eau ayant des points d'ébullition sous pression barométrique supérieurs à 100 °C, ainsi que dans les mélanges de ces solvants et de quantités minoritaires d'eau; (b) d'un polymère hydrophile non hydrosoluble gonflant au contact de l'eau et n'étant pas soluble dans les solvants polaires miscibles à l'eau ayant des points d'ébullition sous pression barométrique supérieurs à 100 °C; et (c) d'un solvant polaire inoffensif miscible à l'eau, dont le point d'ébullition sous pression barométrique est supérieur à 100 °C, ce solvant étant éventuellement mélangé à une quantité minoritaire d'eau. L'une des caractéristiques de cette colle hydrophile autocollante composite est que les polymères (a) et (b) sont remplacés par un copolymère non réticulé de monomères hydrophile et hydrophobe, qui n'est que partiellement soluble dans le constituant (c), mais qui gonfle au contact de celui-ci. On a également prévu un procédé de préparation de ladite colle hydrophile autocollante composite, consistant à soumettre à une agitation intense le polymère pulvérulent sec (a), à savoir le polymère non hydrosoluble gonflant au contact de l'eau et étant soluble dans les solvants polaires miscibles à l'eau ayant des points d'ébullition sous pression barométrique supérieurs à 100 °C, ainsi que dans les mélanges de ces solvants et de quantités minoritaires d'eau, le polymère (b), à savoir le polymère hydrophile non hydrosoluble gonflant au contact de l'eau et n'étant pas soluble dans les solvants polaires miscibles à l'eau ayant des points d'ébullition sous pression barométrique supérieurs à 100 °C, et le constituant (c), à savoir le solvant polaire inoffensif miscible à l'eau, dont le point d'ébullition sous pression barométrique est supérieur à 100 °C, ce solvant étant éventuellement mélangé à une quantité minoritaire d'eau; puis à étaler sur une plaque la pâte ainsi obtenue, et à la laisser durcir jusqu'à obtention d'une couche gélifiée. Le procédé de mise en oeuvre de ladite colle hydrophile autocollante composite consiste avantageusement à mélanger les constituants à une température égale ou inférieure à 15 °C, puis à étaler la masse obtenue sur la surface d'un dispositif à usage médical que l'on souhaite coller à la peau, et à durcir la couche étalée à une température comprise entre 15 et 100 °C environ, et ce soit par stockage prolongé, soit par chauffage.
PCT/CZ1995/000007 1994-05-11 1995-05-10 Colle hydrophile autocollante composite et son procede de preparation WO1995031514A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
SK1276-2000A SK281917B6 (sk) 1994-05-11 1995-05-10 Kompozitné hydrofilné lepidlo citlivé na tlak
DE69503898T DE69503898T2 (de) 1994-05-11 1995-05-10 Druckempfindlicher hydrophiler verbundklebstoff und herstellungsverfahren
EP95917255A EP0759054B1 (fr) 1994-05-11 1995-05-10 Colle hydrophile autocollante composite et son procede de preparation
US08/732,477 US5807917A (en) 1994-05-11 1995-05-10 Composite pressure sensitive hydrophilic adhesive and method of preparing the same
SK1431-96A SK281916B6 (sk) 1994-05-11 1995-05-10 Kompozitné hydrofilné lepidlo citlivé na tlak, spôsob jeho prípravy a spôsob lepenia
JP7529273A JPH10500158A (ja) 1994-05-11 1995-05-10 複合感圧親水性接着剤及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZPV1165-94 1994-05-11
CZ116594 1994-05-11

Publications (1)

Publication Number Publication Date
WO1995031514A1 true WO1995031514A1 (fr) 1995-11-23

Family

ID=5462856

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CZ1995/000007 WO1995031514A1 (fr) 1994-05-11 1995-05-10 Colle hydrophile autocollante composite et son procede de preparation

Country Status (8)

Country Link
US (2) US5807917A (fr)
EP (1) EP0759054B1 (fr)
JP (1) JPH10500158A (fr)
CA (1) CA2191488A1 (fr)
CZ (1) CZ6930U1 (fr)
DE (1) DE69503898T2 (fr)
SK (2) SK281917B6 (fr)
WO (1) WO1995031514A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6719699B2 (en) 2002-02-07 2004-04-13 Sonotech, Inc. Adhesive hydrophilic membranes as couplants in ultrasound imaging applications
US7175897B2 (en) * 2002-12-17 2007-02-13 Avery Dennison Corporation Adhesive articles which contain at least one hydrophilic or hydrophobic layer, method for making and uses for same
US6683280B1 (en) 2003-03-12 2004-01-27 Jeffrey S. Wofford Apparatus and method for prosthesis securement
US20060258788A1 (en) * 2005-05-13 2006-11-16 Scott Coggins Polymeric hydrogel compositions
EP2788444B1 (fr) 2011-12-07 2016-09-28 Bridgestone Corporation Adhésifs aqueux
KR101402693B1 (ko) * 2012-08-09 2014-06-03 박승구 합지 용지 제조 방법 및 합지 용지
JP5993103B2 (ja) 2013-03-14 2016-09-14 ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー 再生剤
CN115716362A (zh) * 2014-07-10 2023-02-28 伊索拉美国有限公司 薄树脂膜及其在铺层中的用途

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0085327A1 (fr) * 1982-01-18 1983-08-10 Medtronic, Inc. Compositions conductrices de l'électricité et électrodes pour l'utilisation de celles-ci

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303066A (en) * 1979-06-28 1981-12-01 National Patent Development Corporation Burn dressing
GB8709498D0 (en) * 1987-04-22 1987-05-28 Bay M Wound dressing
US5468811A (en) * 1989-11-02 1995-11-21 National Patent Development Corporation Hydrophilic composite polymer articles formed from a settable paste comprising a mixture of hydrophilic polymer and unsaturated monomer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0085327A1 (fr) * 1982-01-18 1983-08-10 Medtronic, Inc. Compositions conductrices de l'électricité et électrodes pour l'utilisation de celles-ci

Also Published As

Publication number Publication date
DE69503898D1 (de) 1998-09-10
SK281916B6 (sk) 2001-09-11
CZ6930U1 (cs) 1997-12-29
US6005039A (en) 1999-12-21
EP0759054A1 (fr) 1997-02-26
SK143196A3 (en) 1997-07-09
SK281917B6 (sk) 2001-09-11
JPH10500158A (ja) 1998-01-06
US5807917A (en) 1998-09-15
DE69503898T2 (de) 1998-12-17
EP0759054B1 (fr) 1998-08-05
CA2191488A1 (fr) 1995-11-23

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